The present invention relates to a water and oil repellent composition comprising a specific compound having a polyfluoroalkyl group and a thermoplastic polymer, and a shaped product such as a film or fiber formed from such a composition.
As a shaped product such as a film or fiber having water and oil repellency, and as a composition to be used for its production, a composition comprising a fluoroaliphatic group-containing piperazine compound and a thermoplastic polymer, and a shaped product formed from such a composition (JP-A-6-184354), or a composition comprising a fluoroaliphatic group-containing amino alcohol and a thermoplastic polymer, and a shaped product formed from such a composition (JP-A-6-200073), are, for example, known.
However, with such conventional water and oil repellent compositions, the water and oil repellency was not sufficient, and a composition which is capable of providing better water and oil repellency, has been desired.
It is an object of the present invention to provide a water and oil repellent composition which is capable of imparting excellent water and oil repellency, and a shaped product excellent in water and oil repellency, which contains such a composition.
The present invention has been made to solve the above-mentioned problem and provides a water and oil repellent composition comprising a compound of the following formula (1) (hereinafter referred to also as Compound 1, and other compounds may also be referred to similarly) and a thermoplastic polymer, as essential components: 
where the symbols in the formula (1) have the following meanings:
Rf: a C1-20 polyfluoroalkyl group,
X: (CH2)m, wherein m is an integer of from 1 to 10,
A, A1, A2: each independently, O, S or N(Z3), wherein Z3 is a hydrogen atom or an alkyl group,
Z1: an octadecyl group,
Z2: an alkyl group, or an alkyl group having at least one hydrogen atom substituted,
W: a trivalent organic group, and
a, b: each independently, 1 or 2, provided that a+b is 2 or 3.
Further, the present invention provides a shaped product formed from such a water and oil repellent composition.
Now, the present invention will be described in detail with reference to the preferred embodiments.
In this specification, a polyfluoroalkyl group is represented by a Rf group.
In Compound 1, Rf is a C1-20 linear or branched Rf group.
The carbon number of the Rf group is preferably from 4 to 20, particularly preferably from 4 to 16. If the carbon number of the Rf group is within the above range, the water and oil repellency of Compound 1 is excellent, such being preferred.
The number of fluorine atoms in the R group is preferably at least 60%, particularly preferably at least 80%, when it is represented by the formula of [(number of fluorine atoms in the R group)/(number of hydrogen atoms contained in an alkyl group having the same carbon number as in the Rf group)]xc3x97100(%).
The Rf group may contain halogen atoms other than fluorine atoms. As such other halogen atoms, chlorine atoms are preferred. Further, between the carbon-carbon bond in the Rf group, an etheric oxygen atom or a thioetheric sulfur atom may be inserted.
The structure of the terminal portion of the Rf group may, for example, be xe2x80x94CF3, xe2x80x94CH2H, xe2x80x94CFH2 or xe2x80x94CF2Cl, and xe2x80x94CF3 is particularly preferred.
As the Rf group, a linear group is preferred, and a perfluoroalkyl group (hereinafter referred to also as a RF group) is particularly preferred, since Compound 1 is thereby excellent in water and oil repellency. In Compound 1, X is xe2x80x94(CH2)mxe2x80x94 wherein m is an integer of from 1 to 10. Further, each of A, A1 and A2 is xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94N(Z3)xe2x80x94, wherein Z3 is a hydrogen atom or an alkyl group. A is preferably xe2x80x94Oxe2x80x94.
As Rfxe2x80x94Xxe2x80x94Axe2x80x94 in Compound 1, the following specific examples may preferably be mentioned.
F(CF2)4(CH2)2Oxe2x80x94, F(CF2)6(CH2)2Oxe2x80x94, F(CF2)10(CH2)2Oxe2x80x94, F(CF2)12(CH2)2Oxe2x80x94, F(CF2)14(CH2)2Oxe2x80x94, F(CF2)16(CH2)2Oxe2x80x94, F(CF2)18(CH2)2Oxe2x80x94, F(CF2)20(CH2)2Oxe2x80x94, F(CF2)8(CH2)3Oxe2x80x94, F(CF2)10(CH2)3Oxe2x80x94, F(CF2)12(CH2)3Oxe2x80x94, F(CF2)4(CH2)4Oxe2x80x94, F(CF2)6(CH2)4Oxe2x80x94, F(CF2)8(CH2)6Oxe2x80x94, F(CF2)10(CH2)6Oxe2x80x94, F(CF2)4(CH2)2Sxe2x80x94, H(CF2)12(CH2)3Oxe2x80x94.
In Compound 1, A1 is preferably xe2x80x94Oxe2x80x94 or xe2x80x94Sxe2x80x94. Further, Z1 is an octadecyl group, and a linear octadecyl group is particularly preferred, since it is excellent in water repellency.
In Compound 1, A2 is preferably xe2x80x94Oxe2x80x94 or xe2x80x94N(Z3)xe2x80x94. Z3 is preferably a hydrogen atom or a C1-3 alkyl group, since the synthesis of Compound 1 is thereby easy. Further, Z2 is an alkyl group, or an alkyl group having at least one hydrogen atom substituted. Z2 is preferably a substituted alkyl group having a carbon number of at least 1.
In Compound 1, xe2x80x94A2xe2x80x94Z2 is preferably an alkoxy group, a substituted alkoxy group, a mono- or di-alkylamino group or a substituted alkylamino group. Particularly preferred is a substituted alkoxy group or a substituted amino group. The substituted alkoxy group may preferably be a 2,3-epoxypropoxy group, a 2-cyanoethoxy group, a 2-nitroethoxy group or a 2-hydroxyethoxy group. The substituted amino group may preferably be a hydroxymethylamino group, a 2-hydroxyethylamino group, an aziridinyl group, a bis(2-hydroxyethyl)amino group or a 2-(2,3-epoxypropoxy)ethylamino group.
In Compound 1, W is a trivalent organic residue having three xe2x80x94NCO groups derived from a trifunctional isocyanate compound.
As the trifunctional isocyanate compound, a biuret-modified product of hexamethylene diisocyanate (hereinafter referred to as HDI), an adduct of trimethylolpropane and tolylene diisocyanate (hereinafter referred to as TDI), an adduct of trimethylolpropane and HDI, or an isocyanurate modified product of TDI, HDI or isophorone diisocyanate, may, for example, be mentioned.
Further, each of a and b which are independent of one another, is 1 or 2.
Compound 1 can be synthesized by reacting Rfxe2x80x94Xxe2x80x94Axe2x80x94H and Z1xe2x80x94A1xe2x80x94H and, if necessary, Z2xe2x80x94A2xe2x80x94H, to the above-mentioned trifunctional isocyanate compound. As Compound 1, the following specific examples may be mentioned as preferred. 
In the water and oil repellent composition of the present invention, Compound 1 may be of one type, or two or more types. At that time, the Rf group may be of one type, or two or more types.
The content of Compound 1 in the water and oil repellent composition is preferably from 100 to 10,000 ppm.
In the present invention, the thermoplastic polymer may, preferably, be a polyamide such as nylon 6 or nylon 66, a polyester such as polyethylene terephthalate, a polyolefin such as polyethylene or polypropylene, or a polyurethane.
The water and oil repellent composition of the present invention is prepared by mixing Compound 1 with the thermoplastic polymer in a powder form or in a pellet form. The mixing may be carried out in one step or may be carried out in two steps via a concentrate so-called a master batch. Further, Compound 1 in a state as dissolved or dispersed in a solvent, may be dried to remove the solvent and then mixed with the thermoplastic polymer. The mixing is preferably carried out to be uniform.
The obtained water and oil repellent composition may be melt-extruded to form a shaped product such as a film or fiber. After the melt extrusion, the film or fiber may be subjected to annealing for the purpose of further improving the oil and water repellency. The annealing is preferably carried out for from a few tens seconds to a few minutes at a temperature of not higher than the melting point of the thermoplastic polymer.
Now, the present invention will be described in further detail with reference to Preparation Examples (Examples 1 to 3), Working Examples (Examples 4 to 6) and Comparative Example (Example 7). However, it should be understood that the present invention is by no means restricted to such specific Examples.